Method of manufacturing thermoplastic resin, crosslinked resin, and crosslinked resin composite material

ABSTRACT

Process for production of post-crosslinkable thermoplastic resins by bulk-polymerizing a polymerizable composition (A) comprising (I) a monomer fluid containing a cyclic olefin (α) having two or more metathetical ring-opening reaction sites in the molecule in an amount 10 wt % or above based on the total amount of the monomers or a monomer fluid containing a norbornene monomer and a crosslinking agent, (II) a metathetical polymerization catalyst, and (III) a chain transfer agent; thermoplastic resins obtained by this process. These thermoplastic resins are free from odor due to residual monomers and are excellent in storage stability. Process for producing crosslinked resins and composite materials which comprises laminating the thermoplastic resin to a substrate and then crosslinking the thermoplastic resin. These crosslinked resins and composite materials are invention are excellent in electrical insulation properties, mechanical strength, heat resistance, and dielectric characteristics, and are useful as electrical materials.

This application is a Divisional of application Ser. No. 10/519,228,which has a filing date of Jan. 30, 2006, now U.S. Pat. No. 7,476,716B2, for which priority is claimed under 35 U.S.C. §120. Application Ser.No. 10/519,228 is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP2003/008105 filed on Jun. 26, 2003.This application also claims priority, under 35 U.S.C. §119, toApplications Nos. 2002-190929 filed in Japan on Jun. 28, 2002,2002-219255 filed in Japan on Jul. 29, 2002, and 2003-10967 filed inJapan on Jan. 20, 2003. The entire contents of each of theabove-identified applications are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a post-crosslinkable thermoplasticresin, a method for manufacturing the same, and to a method formanufacturing a crosslinked resin and crosslinked resin compositematerial comprising steps of heating, melting, and crosslinking thethermoplastic resin.

BACKGROUND ART

Conventionally, a method of obtaining a molded product by curing a resinwhich is produced by metathesis polymerization of a cycloolefin and thelike has been known. For example, a method of preparing a thermoplasticresin such as a thermoplastic norbornene resin by solutionpolymerization and crosslinking the thermoplastic resin using acrosslinking agent such as an organic peroxide to obtain a crosslinkedmolded product, a method of reacting cycloolefins which can bepolymerized by metathesis polymerization in the presence of a carbenecomplex such as ruthenium without using a solvent to obtain a half-curedmolded product and laminating a copper foil on the resulting half-curedmolded product by press-heating to obtain a copper-clad laminate, andother methods have been proposed.

As the former method of obtaining a crosslinked molded product, JapanesePatent Application Laid-open No. 6-248164 describes a method comprisingpreparing a homogeneously dispersed norbornene resin composition byadding 0.001-30 parts by weight of an organic peroxide to 100 parts byweight of a thermoplastic hydrogenated ring-opening norbornene resin andadding 0.1-10 parts by weight of a crosslinking agent to one part byweight of the organic peroxide, forming the composition into a film orprepreg, laminating the film or prepreg on another material (substrate),and crosslinking by fusing the resulting laminate by heat-press toobtain a crosslinked molded product. The patent specification describesthat the crosslinked molded product exhibits excellent heat resistance,solvent resistance, chemical resistance, moisture resistance, waterresistance, and electrical properties and is useful as an interlayerdielectric, a film for forming a moisture-proof layer, and the like.

However, the proposed method requires process steps of applying athermoplastic resin composition solution to a substrate, removing thesolvent to obtain a sheet, peeling the sheet from the substrate, andlayering the sheet on a copper foil or the like, followed by a heatpress operation. The method is complicated due to the many process stepsand is not necessarily advantageous for manufacturing on an industrialscale. Moreover, the copper foil may be peeled off due to a residualsolvent or may blister due to a gas generated from the solvent.

As the latter method of manufacturing a copper-clad laminate bymetathesis polymerization of cycloolefins, Japanese Patent ApplicationLaid-open No. 2001-71416 describes a method of preparing a semi-curedcurable molded material by reacting metathesis-polymerizablecycloolefins in the presence of a carbene complex of ruthenium orosmium, placing a copper foil on at least one side of the moldedmaterial, and applying heat-press. This method has made it possible toefficiently manufacture a copper-clad laminate using a press-formingmachine by dividing the process into a first step of obtaining a curablemolding material in a half-cure state in which the polymerization(metathesis) reaction of raw material cycloolefins is not completed anda second step of completely curing the resulting molding material withheating.

However, this method has a drawback of unduly worsening the workingenvironment due to an unacceptable odor of unreacted monomers whenpreparing the half-cured molding material. In addition, the hardness ofthe molding material may change due to a continued polymerizationreaction while the material is stored in the half-cured state, making itdifficult to obtain a copper-clad laminate with a desired form.

Japanese Patent Application Laid-open No. 11-507962 discloses a methodwhich comprises polymerizing cycloolefins in the presence of aruthenium-carbene complex and a crosslinking agent by metathesispolymerization to produce a polycycloolefin and post-curing(post-crosslinking) the polymer.

However, when the method taught by the patent specification is followedby heat-pressing the norbornene resin-copper foil laminate obtained bythis method, only a cross-linking reaction proceeds without the resinbefore the post-cure being melted or fluidized. For this reason, it isdifficult to produce a copper-clad laminate with excellent interlayeradhesion.

In view of this situation, an object of the present invention is toprovide a post-crosslinkable thermoplastic resin and a method formanufacturing the same, the thermoplastic resin being obtainable by bulkpolymerization of cycloolefins in the presence of a metathesispolymerization catalyst, and being free from a problem of an odor due toresidual monomers, excelling in fluidity during melting with heating,and storage stability, Another object of the present invention is toprovide a crosslinked resin and a method for manufacturing the same, theresin being obtained by crosslinking the above thermoplastic resin andexcelling in electric insulation properties, mechanical strength, heatresistance, dielectric property, and the like. Still another object ofthe present invention is to provide a method for manufacturing acrosslinked resin composite material, and the composite material beingobtained by laminating the thermoplastic resin of the present inventionon a substrate and crosslinking the thermoplastic resin, excelling inadhesion between the crosslinked resin and substrate, and useful as anelectrical material and the like.

DISCLOSURE OF THE INVENTION

To achieve the above objects, the present inventor has conductedextensive studies on the method for efficiently producing apost-crosslinkable thermoplastic resin by bulk polymerization ofcycloolefins or norbornene monomers in the presence of a metathesispolymerization catalyst.

As a result the present inventor has found that (i) a post-crosslinkablethermoplastic resin being free from a problem of an odor due to residualmonomers, excelling in fluidity during melting with heating, andexcelling in storage stability can be efficiently produced bypolymerizing a monomer solution containing 10 wt % or more, based on thetotal amount of monomers, of a cycloolefin (α) which has two or moremetathesis ring-opening reaction sites in the molecule, or a monomersolution containing a norbornene monomer and a crosslinking agent, bybulk polymerization in the presence of a metathesis polymerizationcatalyst and a chain transfer agent, (ii) a crosslinked resin excellingin electric insulation properties, mechanical strength, heat resistance,dielectric property, and the like can be efficiently obtained bycrosslinking the above thermoplastic resin, and (iii) a crosslinkedresin composite material excelling in adhesion can be efficientlyobtained by laminating the thermoplastic resin on a substrate andcrosslinking the thermoplastic resin. These findings have led to thecompletion of the present invention.

Specifically, in the first place, the present invention provides amethod for manufacturing a post-crosslinkable thermoplastic resincomprising polymerizing a polymerizable composition (A) by bulkpolymerization, the polymerizable composition (A) comprising:

(I) a monomer solution containing 10 wt % or more, based on the totalamount of monomers, of a cycloolefin (α) which has two or moremetathesis ring-opening reaction sites in the molecule, or a monomersolution containing a norbornene monomer and a crosslinking agent,

(II) a metathesis polymerization catalyst, and

(III) a chain transfer agent.

Therefore, the method for manufacturing the thermoplastic resin of thepresent invention comprises either

(1) polymerizing a polymerizable composition (A) comprising a monomersolution containing 10 wt % or more, based on the total amount ofmonomers, of a cycloolefin (α) which has two or more metathesisring-opening reaction sites in the molecule, a metathesis polymerizationcatalyst, and a chain transfer agent by bulk polymerization, or

(2) polymerizing a polymerizable composition (A) comprising a norbornenemonomer, a metathesis polymerization catalyst, a chain transfer agent,and a crosslinking agent by bulk polymerization.

In the method of manufacturing the thermoplastic resin of the presentinvention, the maximum temperature during the bulk polymerization ispreferably less than 230° C. and the polymerization reaction rate ispreferably 80% or more.

In the method of manufacturing the thermoplastic resin of the presentinvention, the above-mentioned chain transfer agent is preferably acompound represented by the formula: CH₂═CH-Q, wherein Q is a groupwhich has at least one group selected from the group consisting of amethacryloyl group, acryloyl group, vinyl silyl group, epoxy group, andamino group.

In the method of manufacturing the thermoplastic resin of the presentinvention according to (1) above, dicyclopentadiene is preferably usedas the cycloolefin (α).

In the method of manufacturing the thermoplastic resin of the presentinvention according to (2) above, a norbornene monomer mixture whichcontains a norbornene monomer having a carboxyl group or anacid-anhydride group as the norbornene monomer is preferably used and anepoxy compound is preferably used as the crosslinking agent. As anotherexample of the method of manufacturing the thermoplastic resin accordingto (2) above, the bulk polymerization of a polymerizable composition (A)is preferably carried out using a radical generating agent as thecrosslinking agent and at a reaction temperature below the one-minutehalf-life temperature of the radical generating agent, and morepreferably further using a radical crosslinking retarder as a componentof the polymerizable composition (A).

In the second place, the present invention provides the postcrosslinkable thermoplastic resin produced by the method of the presentinvention.

The thermoplastic resin of the present invention that can be obtained bythe bulk polymerization of the above-mentioned polymerizable composition(A) on a support and molded into the film form is preferable. Thesupport is preferably a metal foil or resin film.

The thermoplastic resin that can be obtained by the bulk polymerizationof the above-mentioned polymerizable composition (A) in a mold andmolded into a prescribed form is also preferable in the presentinvention.

The thermoplastic resin that can be obtained by impregnating a textilematerial with the above-mentioned polymerizable composition (A) andpolymerizing the polymerizable composition (A) by bulk polymerization isalso preferable.

In the third place, the present invention provides a method formanufacturing a crosslinked resin comprising a step of crosslinking thethermoplastic resin of the present invention.

In the fourth place, the present invention provides a method formanufacturing a crosslinked resin composite material comprising a stepof laminating the thermoplastic resin of the present invention andcrosslinking the thermoplastic resin portion.

In the process for producing the crosslinked resin composite material ofthe present invention, a metal foil is preferably used as the substratematerial. Use of a metal foil treated with a silane coupling agent ofthe following formula (1) or a thiol coupling agent of the followingformula (2) is more preferable.RSiXYZ  (1)T(SH)_(n)  (2)wherein R is a group having a double bond, a mercapto group, or an aminogroup at the terminal, X and Y individually represent a hydrolyzablegroup, a hydroxyl group, or an alkyl group, Z represents a hydrolyzablegroup or a hydroxyl group, T represents an aromatic ring, an aliphaticring, a heterocyclic, or an aliphatic chain, and n is an integer of 2 ormore.

In the method of manufacturing the crosslinked resin composite materialof the present invention, a printed circuit board is preferably used asthe substrate.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below in the followingsections:

-   1) the method of manufacturing the post-crosslinkable thermoplastic    resin and the thermoplastic resin produced by this method, 2) the    method of manufacturing the crosslinked resin, and 3) the method of    manufacturing the crosslinked resin composite material.-   1) Method of Manufacturing Post-Crosslinkable Thermoplastic Resin    and the Thermoplastic Resin

The method of manufacturing post-crosslinkable thermoplastic resin ischaracterized by polymerizing the polymerizable composition (A) whichcomprises (I) a monomer solution containing 10 wt % or more, based onthe total amount of monomers, of a cycloolefin (α) having two or moremetathesis ring-opening reaction sites in the molecule, or a monomersolution containing a norbornene monomer and a crosslinking agent, (II)a metathesis polymerization catalyst, and (III) a chain transfer agentby bulk polymerization.

(I) Monomer Solution

In the present invention, either a monomer solution containing 10 wt %or more, based on the total amount of monomers, of a cycloolefin (α)having two or more metathesis ring-opening reaction sites in themolecule (hereinafter referred to as “monomer solution 1”) or a monomersolution containing a norbornene monomer and a crosslinking agent(hereinafter referred to as “monomer solution 2”) is used as the monomersolution.

(Monomer Solution 1)

The monomer solution 1 comprises a cycloolefin (α) having two or moremetathesis ring-opening reaction sites in the molecule in an amount of10 wt % or more of the total amount of monomers.

The cycloolefin (α) is an olefin compound with a ring structure havingtwo or more metathesis ring-opening reaction sites in the molecule. Themetathesis ring-opening reaction site herein indicates the site of acarbon-carbon double bond in a cyclic structure, in which the doublebond cleaves by the metathesis reaction accompanied by ring opening.

As examples of the olefin compound with a cyclic structure having ametathesis ring-opening reaction site, a compound having a cyclobutenering, cyclopentene ring, cyclohexene ring, cycloheptene ring,cyclooctene ring, cyclododecene ring, bicyclo[2.2.1]heptene ring, or thelike can be given.

As examples of the cycloolefin (α), a monocyclic compound with one typeof the cyclic structure having a metathesis ring-opening reaction site,a condensed cyclic compound with one or more types of the cyclicstructure, and a polycyclic compound with one or more types of thecyclic structure combined together.

Although there are no specific limitations to the number of carbon atomspossessed by the cycloolefin (α), the number of carbon atoms is usually7-30, and preferably 7-20. There are also no specific limitations to thenumber of the metathesis reaction sites in the cycloolefin (α) in so faras two or more such sites are present The number is usually 2-5, andpreferably 2-4.

It is preferable in the cycloolefin (α) used in the present inventionthat the above-mentioned at least two or more metathesis ring-openingreaction sites are present in different rings, each having a differentcyclic structure from the other. Since the reactivity of onering-opening reaction site in this type of cycloolefin (α) differs fromthe reactivity of the other such site, it is possible to cause the onering-opening reaction site to be solely involved in the ring-openingreaction and to preserve the other site unreacted in the resultingthermoplastic resin for the metathesis crosslinking reaction in thepost-crosslinking stage. This ensures efficient production ofpost-crosslinkable thermoplastic resin containing only a small amount ofresidual monomers (resulting in a high polymerization reaction rate) andexcelling in storage stability.

The following compounds (a)-(c) can be given as specific examples of thecycloolefin (α).

(a) Condensed cyclic compounds having the same or different condensedcycloolefin rings such aspentacyclo[6.5.1.1^(3,6)0.0^(2,7)0.0^(9,13)]pentadeca-4,10-diene,pentacyclo[9.2.1.1^(4,7)0.0^(2,10)0.0^(3,8)]pentadeca-5,12-diene,dicyclopentadiene, tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodeca-4,9-diene,tricyclo[12.2.1.0^(2,13)]heptadeca-5,9,15-triene,tetracyclo[9.2.1.0^(2,10)0.0^(4,8)]tetradeca-5,12-diene,pentacyclo[9.2.1.1^(3,9)0.0^(2,10)0.0^(4,8)]pentadeca-5,12-diene,norbornadiene, bicyclo[6.2.0]deca-4,9-diene,bicyclo[6.3.0]undeca-4,9-diene, andtricyclo[8.2.1.0^(2,9)]trideca-5,11-diene.

(b) Polycyclic compounds formed by single bond of the same or differentcycloolefin rings such as9-cyclohexenyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-cyclopentenyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene,5,5′-bi-(2-norbornene), 5-cyclooctenyl-2-norbornene,5-norbornene-2-carboxylate-3-cyclopenten-1-yl, and5-norbornene-2-carboxylate-5-norbornen-2-yl.

(c) Compounds having at least one substituent at any site of the abovecompounds (a) or (b), the substituents being selected from the groupconsisting of an alkyl group such as a methyl group, ethyl group,n-propyl group, isopropyl group, and n-butyl group; an alkylidene groupsuch as a methylidene group, ethylidene group, propylidene group, andbutylidene group; an aromatic hydrocarbon group such as a phenyl groupand naphthyl group; a carboxyl group; an alkoxycarbonyl group such as amethoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, andbutoxycarbonyl group; an acid anhydride group; and a cyano group.

These compounds may be used either individually or in combination of twoor more.

Among these compounds, dicyclopentadiene is a particularly preferablecycloolefin (α) from the viewpoints of easy availability, metathesispolymerization reaction rate, and capability of producing athermoplastic resin with excellent storage stability.

The amount of cycloolefin (α) is 10 wt % or more, preferably 20 wt % ormore, and still more preferably 30 wt % or more of the total amount ofmonomers. If the amount of the cycloolefin (α) is less than 10 wt %,post-crosslinking is difficult.

In addition to the cycloolefin (α), a cycloolefin (β) having onemetathesis ring-opening reaction site in the molecule can be added tothe monomer solution 1.

Specific preferable examples of the cycloolefin (β) are norbornenemonomers; monocycloolefins such as cyclobutene, cyclooctene,1,5-cyclooctadiene; and the like. These cycloolefins may be substitutedwith a hydrocarbon group such as an alkyl group, alkenyl group,alkylidene group, or aryl group, or a polar group.

Given as specific examples of norbornene monomers aretetracyclododecenes such astetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-methyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-ethyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-cyclohexyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-cyclopentyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-methylenetetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-ethylidenetetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-vinyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-propenyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,9-phenyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, methyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-carboxylate,4-methyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-carboxylate,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-methanol,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-ol,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-carboxylic acid,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4,5-carboxylic acid,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4,5-dicarboxylic acidanhydride, tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-nitrile,tetracyclo[6.2.1.1^(3.6)0.0^(2,7)]dodec-9-ene-4-carbaldehyde,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-carboxamide,tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4,5-dicarboxylic acidimide, 9-chlorotetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene,4-trimethoxysilyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene,9-acetyltetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene; norbornenes suchas tricyclo[5.2.1.0^(2,6)]-dec-8-ene, 2-norbornene,5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene,5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene,5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene,5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-phenyl-2-norbornene,tetracyclo[9.2.1.0^(2,10)0.0^(3,8)]tetradeca-3,5,7,12-tetraene (alsoknown as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene),tetracyclo[10.2.1.0^(2,11)0.0^(4,9)]pentadeca-4,6,8,13-tetraene (alsoknown as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene), methyl5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, methyl2-methyl-5-norbornene-2-carboxylate, ethyl2-methyl-5-norbornene-2-carboxylate, 5-norbornen-2-yl acetate,2-methyl-5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate,5-norbornen-2-yl methacrylate, 5-norbornene-2-carboxylate,5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylateanhydride, 5-norbornene-2-methanol, 5-norbornene-2,3-dimethanol,5-norbornene-2,2-dimethanol, 5-norbornene-2-ol, 5-norbornene-2-nitrile,5-norbornene-2-carbaldehyde, 5-norbornene-2-carboxamide,2-acetyl-5-norbornene, and 3-methoxycarbonyl-5-norbornene-2-carboxylate;oxanorbornenes such as 7-oxa-2-norbornene, 5-methyl-7-oxa-2-norbornene,5-ethyl-7-oxa-2-norbornene, 5-butyl-7-oxa-2-norbornene,5-hexyl-7-oxa-2-norbornene, 5-cyclohexyl-7-oxa-2-norbornene,5-ethylidene-7-oxa-2-norbornene, 5-phenyl-7-oxa-2-norbornene, methyl7-oxa-5-norbornene-2-carboxylate, 7-oxa-5-norbornen-2-yl acetate, and7-oxa-5-norbornen-2-yl methacrylate; and 5-member or more cycloolefinssuch ashexacyclo[6.6.1.1^(3,6).1^(10,13)0.0^(2,7)0.0^(9,14)]heptadec-4-ene.

These compounds may be used either individually or in combination of twoor more as the cycloolefin (β).

(Monomer Solution 2)

Monomer solution 2 comprises a norbornene monomer and a crosslinkingagent.

As the norbornene monomer, any norbornene monomers given as examples ofthe cycloolefin (β) can be used. In addition, any compounds having abicyclo[2.2.1]heptene ring given as examples of the cycloolefin (α) canalso be used.

Either one norbornene monomer or a mixture of two or more norbornenemonomers can be used. It is possible to freely control the glasstransition temperature and melting point of the thermoplastic resin bychanging the ratio of the two or more norbornene monomers used incombination.

In addition, a norbornene monomer mixture prepared by adding amonocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene,cyclododecene, and 1,5-cyclooctadiene or a derivative of thesemonocyclic cycloolefins having a substituent can also be used as themonomer solution 2. The amount of monocyclic cycloolefins and theirderivatives is preferably 40 wt % or less, and more preferably 20 wt %or less of the total amount of norbornene monomers. If more than 40 wt%, the polymer obtained by bulk polymerization may be an elastomerinstead of a resin.

Of the above monomers, when an epoxy compound is used as thecrosslinking agent, a norbornene monomer mixture which contains anorbornene monomer having a carboxyl group or an acid-anhydride group asthe norbornene monomer is preferably used due to easy production of acrosslinked resin. The content of the norbornene monomer having acarboxyl group or an acid-anhydride group in the above norbornenemonomer mixture is preferably 1 mol % or more, and more preferably 5 mol% or more.

The crosslinking agent used in the present invention causes acrosslinking reaction with the functional group of the thermoplasticresin produced by bulk polymerization of norbornene monomers to producea crosslinked resin. As examples of the functional group, acarbon-carbon double bond, carboxylic acid group, acid anhydride group,hydroxyl group, amino group, active halogen atom, and epoxy group can begiven.

As examples of the crosslinking agent, a radical generating agent, epoxycompound, isocyanate group-containing compound, carboxylgroup-containing compound, acid anhydride group-containing compound,amino-group containing compound, and Lewis acid can be given. Thesecrosslinking agents may be used either individually or in combination oftwo or more. Of these, a radical generating agent, epoxy compound,isocyanate group-containing compound, carboxyl group-containingcompound, and acid anhydride group-containing compound are preferable. Aradical generating agent, epoxy compound, and isocyanategroup-containing compound are more preferable crosslinking agents, witha radical generating agent or epoxy compound being particularlypreferable.

As examples of the radical generating agent, organic peroxides and azocompounds can be given. Examples of the organic peroxide include, butare not limited to, hydroperoxides such as t-butyl hydroperoxide,p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxidessuch as dicumyl peroxide, t-butyl cumyl peroxide,α,α′-bis(t-butylperoxy-m-isopropyl)benzene, di-t-butylperoxide,2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine,2,5-dimethyl-2,5-di(t-butylperoxy)hexane; diacyl peroxides such asdipropionyl peroxide and benzoyl peroxide; peroxyketals such as2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexin-3,1,3-di(t-butylperoxyisopropyl)benzene;peroxy esters such as t-butylperoxy acetate and t-butylperoxy benzoate;peroxycarbonate such as t-butylperoxy isopropylcarbonate anddi(isopropylperoxy)dicarbonate; ketone peroxides; andalkylsilylperoxides such as t-butyltrimethylsilyl peroxide. Of these,dialkyl peroxides are preferable due to a small hindrance to themetathesis polymerization reaction.

Examples of the diazo compound include4,4′-bisazidobenzal(4-methyl)cyclohexanone, 4,4′-diazidochalcone,2,6-bis(4′-azidobenzal)cyclohexanone,2,6-bis(4′-azidobenzal)-4-methylcyclohexanone,4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane,2,2′-diazidostilbene, and the like.

As the epoxy compound, compounds having two or more epoxy groups in themolecule, for example, a phenol novolak epoxy compound, cresol novolakepoxy compound, cresol epoxy compound, glycidyl ether-type epoxycompounds such as bisphenol A epoxy compound, bisphenol F epoxycompound, brominated bisphenol A epoxy compound, brominated bisphenol Fepoxy compound, and hydrogenated bisphenol A epoxy compound; polyvalentepoxy compounds such as an alicyclic epoxy compound, glycidyl esterepoxy compound, glycidyl amine epoxy compound, and isocyanurate epoxycompound, and the like can be given.

As the isocyanate group-containing compound, compounds having two ormore isocyanate groups in the molecule such as p-phenylene diisocyanate,2,6-toluene diisocyanate, hexamethylene diisocyanate, and the like canbe given.

As examples of the carboxyl group-containing compound, compounds havingtwo or more carboxyl groups such as fumaric acid, phthalic acid, maleicacid, trimellitic acid, himic acid, terephthalic acid, isophthalic acid,adipic acid, and sebacic acid can be given.

As specific examples of the acid anhydride group-containing compounds,maleic anhydride, phthalic anhydride, pyromellitic anhydride,benzophenone tetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and maleic anhydride-modified polypropylene canbe given.

As the Lewis acid, silicon tetrachloride, hydrochloric acid, sulfuricacid, ferric chloride, aluminum chloride, stannic chloride, titaniumtetrachloride, and the like can be given.

As the amino group-containing compound, compounds having two or moreamino groups in the molecule, for example, aliphatic diamines such astrimethyl hexamethylenediamine, ethylenediamine, and 1,4-diaminobutane,aliphatic polyamines such as triethylene tetramine, pentaethylenehexamine, and aminoethyl ethanolamine, aromatic amines such asphenylenediamine, 4,4′-methylenedianiline, toluenediamine, anddiaminoditolyl sulfone can be given.

In the present invention, the type of crosslinking agent to be used canbe properly selected according to the position to be bridged(crosslinking position) in the thermoplastic resin. For example, whenthe polymer molecules are bridged at the carbon-carbon double bond, aradical generating agent can be used. When the thermoplastic resinhaving a carboxyl group or an acid-anhydride group is bridged, an epoxycompound can be used. When the thermoplastic resin having a hydroxylgroup is bridged, a compound having an isocyanate group can be used.When the thermoplastic resin having an epoxy group is bridged, acompound having a carboxyl group or an acid-anhydride group can be used.In addition, Lewis acid can also be used as a crosslinking agent forcationically bridging the molecules.

There are no specific limitations to the amount of the crosslinkingagent. Such an amount can be appropriately determined according to thekind of the crosslinking agent used. When a radical generating agent isused as a crosslinking agent, the amount of the crosslinking agent usedis usually 0.1-10 parts by weight, and preferably 0.5-5 parts by weightfor 100 parts by weight of the norbornene monomers. When an epoxycompound is used as a crosslinking agent, the amount of the crosslinkingagent used is usually 1-100 parts by weight, and preferably 5-50 partsby weight for 100 parts by weight of the norbornene monomers. If theamount of the crosslinking agent is too small, crosslinking isinsufficient and a crosslinking resin with a high crosslinking densitymay not be obtained. If too much an amount is used, not only does thecrosslinking effect reach saturation, there is also a possibility thatthe thermoplastic resin and the crosslinked resin having desiredproperties cannot be obtained.

In the present invention, a crosslinking adjuvant can be used incombination with the crosslinking agent to improve the crosslinkingeffect. Conventionally known crosslinking adjuvants can be used withoutany specific limitations. As examples, dioxime compounds such asp-quinone dioxime, methacrylate compounds such as lauryl methacrylateand trimethylolpropane trimethacrylate, fumaric acid compounds such as adiallyl fumarate, phthalic acid compounds such as a diallyl phthalate,cyanuric acid compounds such as triallyl cyanulate, and imide compoundsuch as maleimide can be given. Although there are no specificlimitations, the amount of the crosslinking adjuvant used is usually0-100 parts by weight, and preferably 0-50 parts by weight for 100 partsby weight of the norbornene monomers.

When a radical generating agent is used as a crosslinking agent in thepresent invention, it is a preferable to add a radical crosslinkingretarder to the polymerizable composition (A). The radical crosslinkingretarder is a compound generally having a radical capture function andexhibits the effect of delaying the radical crosslinking reaction causedby a radical generating agent. Flowability of the thermoplastic resin incase of laminating the resin and storage stability of the thermoplasticresin can be improved by adding a radical crosslinking retarder to thepolymerizable composition (A).

As examples of the radical crosslinking retarder, alkoxy phenols such as4-methoxyphenol, 4-ethoxyphenol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl4-hydroxyanisole, and 3,5-di-t-butyl-4-hydroxyanisole; hydroquinonessuch as hydroquinone, 2-methylhydroquinone, 2,5-dimethylhydroquinone,2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone,2,5-di-t-amylhydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, and2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone; catechols such ascatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol; andbenzoquinones such as benzoquinone, naphthoquinone, andmethylbenzoquinone can be given. Of these, alkoxy phenols, catechols,and benzoquinones are preferable, with the alkoxy phenols beingparticularly preferable.

The amount of the radical crosslinking retarder is usually 0.001-1 mol,and preferably 0.01-1 mol for 1 mol of radical generating agent

(II) Metathesis Polymerization Catalyst

There are no specific limitations to the metathesis polymerizationcatalyst used in the present invention to the extent that the catalystcan polymerize the above-mentioned cycloolefin (α) and norbornenemonomer by the metathesis ring-opening polymerization. As the metathesispolymerization catalyst that can be used, a complex formed from aplurality of ions, atoms, polyatomic ions, and/or compounds bonded to atransition metal atom as the center atom can be given. As the transitionmetal atom, the atoms of groups V, VI, and VIII (in a long periodic-typeperiodic table, hereinafter the same) can be used. Although there are nospecific limitations to the atoms belonging to each group, examplesinclude tantalum as the group V atom, molybdenum and tungsten as thegroup VI atom, and ruthenium and osmium as the group VI atom.

Of these, ruthenium and osmium of the group VIII metal are preferable asthe complex for the metathesis polymerization catalyst, with aruthenium-carbene complex being particularly preferred. Due to excellentcatalyst activity in bulk polymerization, the ruthenium-carbene complexexhibits excellent productivity when applied to the production of apost-crosslinkable thermoplastic resin. A thermoplastic resin withalmost no unfavorable odor (originating from unreacted monomers) can bemanufactured with excellent productivity. In addition, since thecatalyst is comparatively stable and is not easily deactivated in oxygenor moisture in the air, the thermoplastic polymer can be manufacturedunder atmospheric conditions using the catalyst.

The ruthenium-carbene complex is a compound represented by the followingformulas (3) and (4).

wherein R¹ and R² individually represent a hydrogen atom, a halogenatom, or a hydrocarbon group having 1-20 carbon atoms which may containa halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorusatom, or silicon atom. X¹ and X² individually represent an anionicligand. L¹ and L² individually represent a hetero atom-containingcarbene compound or a neutral electron-donating compound. R¹, R², X¹,X², L¹, and L² groups may bond in any optional combination to form amultidentate chelated ligand.

The hetero atom is an atom of the Group XV or XVI in the Periodic Table.Specific examples include N, O, P, S, As, and Se. Of these, N, O, P, S,and the like are preferable, and N is particularly preferable, because astable carbene compound can be obtained.

A hetero atom-containing carbene compound having hetero atoms bonding toboth sides of the carbene carbon atom is preferable, with a carbenecompound having a hetero ring which includes a carbene carbon atom andhetero atoms on both sides of the carbon atom being more preferable. Itis desirable that hetero atoms adjacent to a carbene atom have a bulkysubstituent.

As examples of such hetero atom containing carbene compounds, compoundsshown by the following formulas (5) and (6) can be given:

wherein R³ to R⁶ individually represent a hydrogen atom, a halogen atom,or a hydrocarbon group having 1-20 carbon atoms which may contain ahalogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom,or silicon atom. R³ to R⁶ may be bonded in any optional combination toform a ring.

Specific examples of the compound of the formula (5) or (6) include1,3-dimesitylimidazolidin-2-ylidene,1,3-di(1-adamantyl)imidazolidin-2-ylidene,1-cyclohexyl-3-mesitylimidazolidin-2-ylidene,1,3-dimesityloctahydrobenzimidazol-2-ylidene,1,3-diisopropyl-4-imidazolin-2-ylidene,1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene, and1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene.

In addition to the compounds represented by the above formula (5) or(6), other hetero atom containing carbene compounds such as1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene,1,3-dicyclohexylhexahydropyrimidin-2-ylidene,N,N,N′N′-tetraisopropylformalidinylidene,1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, and3-(2,6-diisopropylphenyl)-2,3-dihydrothiazol-2-ylidene can be used.

In the above formulas (3) and (4), the anionic ligands X¹ and X² areligands having a negative charge when separated from the central metal.Examples of the ligands include halogen atoms such as a fluorine atom,chlorine atom, bromine atom, and iodine atom; a diketonate group,substituted cyclopentadienyl group, alkoxy group, aryloxy group, andcarboxyl group. Of these, halogen atoms are preferable, and a chlorineatom is more preferable.

A neutral electron-donating compound may be any ligand having a neutralcharge when separated from the central metal. Specific examples includecarbonyls, amines, pyridines, ethers, nitrites, esters, phosphines,thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates.Of these, phosphines, ethers, and pyridines are preferable, andtrialkylphosphine is more preferable.

Examples of the complex compound of the formula (3) include rutheniumcomplex compounds in which a hetero atom-containing compound and aneutral electron-donating compound are bonded such asbenzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride,(1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(ticyclopentylphosphine)ruthenium dichloride,benzylidene(1,3-dimesityl-octahydrobenzimidazol-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride,benzylidene[1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene](tricyclohexylphosphine)ruthenium dichloride,benzylidene(1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride,benzylidene(tricyclohexylphosphine)(1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene)rutheniumdichloride,(1,3-diisopropylhexahydropyrimidin-2-ylidene)(ethoxymethylene)(tricyclohexylphosphine)ruthenium dichloride,benzylidene(1,3-dimesitylimidazolidin-2-ylidene)pyridinerutheniumdichloride, (1,3-dimesitylimidazolidin-2-ylidene)(2-phenylethylidene)(tricyclohexylphosphine)ruthenium dichloride, and(1,3-dimesityl-4-imidazolin-2-ylidene)(2-phenylethylidene)(tricyclohexylphosphine)ruthenium dichloride; ruthenium compounds inwhich two neutral electron-donating compounds are bonded such asbenzylidenebis(tricyclohexylphosphine)ruthenium dichloride and(3-methyl-2-buten-1-ylidene)bis(tricyclopentylphosphine)rutheniumdichloride; and ruthenium complex compounds in which two heteroatom-containing carbene compounds are bonded such asbenzylidenebis(1,3-dicyclohexylimidazolidin-2-ylidene)rutheniumdichloride andbenzylidenebis(1,3-diisopropyl-4-imidazolin-2-ylidene)rutheniumdichloride.

As examples of the complex compound of the formula (3) in which R¹ andL¹ bond, compounds shown by the following formulas (7) to (9) can begiven.

Examples of the complex compound of the formula (4) include(1,3-dimesitylimidazolidin-2-ylidene)(phenylvinylidene)(tricyclohexylphosphine)ruthenium dichloride,(t-butylvinylidene)(,3-diisopropyl-4-imidazolin-2-ylidene)(tricyclopentylphosphine)ruthenium dichloride, andbis(1,3-dicyclohexyl-4-imidazolin-2-ylidene)phenylvinylidenerutheniumdichloride.

These ruthenium complex catalysts can be produced by the methodsdescribed in Org. Lett., 1999, Vol. 1, p. 953 and Tetrahedron. Lett.,1999, Vol. 40, p. 2247, for example.

The metathesis polymerization catalyst is used at a molar ratio of themetal atoms in the catalyst to the cycloolefins of 1:2,000 to1:2,000,000, preferably 1:5,000 to 1:1,000,000, and more preferably1:10,000 to 1:500,000.

If necessary, the metathesis polymerization catalyst may be useddissolved or suspended in a small amount of inert solvent. Examples ofthe solvent include chain aliphatic hydrocarbons such as n-pentane,n-hexane, n-heptane, liquid paraffin, mineral spirit; alicyclichydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane,dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane,diethylcyclohexane, decahydronaphthalene, dicycloheptane,tricyclodecane, hexahydroindene cyclohexane, and cyclooctane; andaromatic hydrocarbons such as benzene, toluene, and xylene,nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, andacetonitrile; and oxygen-containing hydrocarbons such as diethyl etherand tetrahydrofuran. Of these, common industrial solvents such asaromatic hydrocarbons, aliphatic hydrocarbons, and alicyclichydrocarbons are preferably used. In addition, a liquid agingpreventive, plasticizer, or elastomer may be used as a solvent to theextent not reducing the activity of the metathesis polymerizationcatalyst.

An activator (co-catalyst) may be used in combination with themetathesis polymerization catalyst to control the polymerizationactivity or to increase the rate of the polymerization reaction. As theactivator, an alkyl compound, a halide, an alkoxy compound, an aryloxycompound, and the like of aluminum, scandium, tin, titanium, orzirconium can be given.

Specific examples of the activator include trialkoxy aluminum,triphenoxy aluminum, dialkoxyalkyl aluminum, alkoxydialkyl aluminum,trialkyl aluminum, dialkoxy aluminum chloride, alkoxyalkyl aluminumchloride, dialkyl aluminum chloride, trialkoxy scandium, tetraalkoxytitanium, tetraalkoxy tin, and tetraalkoxy zirconium.

The activator is used at a molar ratio of the metal atoms in themetathesis polymerization catalyst to the activator of 1:0.05 to 1:100,preferably 1:0.2 to 1:20, and more preferably 1:0.5 to 1:10.

When the complex of a transition metal atom of Group V or Group VI isused as a metathesis polymerization catalyst, it is desirable that boththe metathesis polymerization catalyst and activator are dissolved inthe monomers. However, it is possible to dissolve or suspend themetathesis polymerization catalyst and activator in a small amount ofsolvent to the extent that properties of the resulting products are notimpaired in substance.

(III) Chain Transfer Agent

In the manufacturing method of the present invention, a chain transferagent is used as a component of the polymerizable composition (A). Athermoplastic resin can be obtained by polymerizing the monomers in thepresence of a chain transfer agent.

As the chain transfer agent, a chain olefin which may have asubstituent, for example, can be used. Specific examples includealiphatic olefins such as 1-hexene and 2-hexene; olefins having anaromatic group such as styrene, divinylbenzene, and stilbene; olefinshaving an alicyclic hydrocarbon group such as vinyl cyclohexane; vinylethers such as ethyl vinyl ether; vinyl ketones such as methyl vinylketone, 1,5-hexadien-3-on, 2-methyl-1,5-hexadien-3-on; compoundsrepresented by the formula CH₂CH-Q, wherein Q is a group which has atleast one group selected from the group consisting of a methacryloylgroup, acryloyl group, vinyl silyl group, epoxy group, and amino group.Of these, compounds represented by the formula CH₂═CH-Q is preferable,because the group Q is introduced into the polymer terminals andcontributes to crosslinking of the polymer, thereby increasing thecrosslinking density.

As specific examples of the compound represented by the formulaCH₂═CH-Q, compounds in which Q has a methacryloyl group such as vinylmethacrylate, allyl methacrylate, 3-buten-1-yl methacrylate,3-buten-2-yl methacrylate, and styryl methacrylate; compounds in which Qhas an acryloyl group such as allyl acrylate, 3-buten-1-yl acrylate,3-buten-2-yl acrylate, 1-methyl-3-buten-2-yl acrylate, styryl acrylate,and ethylene glycol diacrylate; compounds in which Q has a vinyl silylgroup such as allyl trivinyl silane, allyl methyl divinyl silane, andallyl dimethyl vinyl silane; compounds in which Q has an epoxy groupsuch as glycidyl (metha)acrylate and allyl glycidyl ether; and compoundsin which Q has an amino group such as allylamine,2-(diethylamino)ethanol vinyl ether, 2-(diethylamino)ethyl acrylate,4-vinylaniline; can be given.

The amount of the chain transfer agent to be added is usually 0.01-10 wt%, and preferably 0.1-5 wt % of the total amount of the monomersolution. The amount of the chain transfer agent in this range ensures ahigh polymerization conversion ratio and efficient production ofpost-crosslinkable thermoplastic resin. If the amount of the chaintransfer agent is too small, a thermoplastic resin may not be produced.If the amount of the chain transfer agent is too large,post-crosslinking may be difficult.

A thermoplastic resin can be manufactured by preparing the polymerizablecomposition (A) which contains the monomer solution 1 or the monomersolution 2 (hereafter may be collectively called “monomer solutions”),the metathesis polymerization catalyst, and the chain transfer agent,and polymerizing the composition (A) by bulk polymerization.

Although there are no specific limitations to the method of preparingthe polymerizable composition (A), a method of separately preparingmonomer solutions and a catalyst solution in which a metathesispolymerization catalyst is dissolved or dispersed in a suitable solvent,and combining the monomer solutions and catalyst solution immediatelybefore polymerization can be given as an example. In this instance, thechain transfer agent may be added either to the monomer solutions or thecatalyst solution, or may be added after the monomer solutions and thecatalyst solutions are mixed. The crosslinking agent may be added to thecatalyst solution without being included in the monomer solutions or maybe added after norbornene monomers are mixed with the catalystsolutions.

Various additives, for example, a reinforcing material, modifier,antioxidant, flame retardant, filler, coloring agent, and lightstabilizer can be added to the polymerizable composition (A). Theseadditives may be dissolved or dispersed in the monomer solutions or thecatalyst solutions beforehand.

As examples of the reinforcing material, glass fiber woven, glassfabric, paper substrate, and nonwoven glass fabric can be given. Asexamples of the modifier, elastomers such as natural rubber,polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR),styrene-butadiene-styrene block copolymer (SBS),styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-dieneterpolymer (EPDM), ethylene-vinyl-acetate copolymer (EVA), and theirhydrogenated products can be given. As examples of the antioxidantvarious antioxidants for plastic rubbers of a hindered phenol-type,phosphorus-type, amine-type, and the like can be given. Theseantioxidants can be used either individually or in combination of two ormore.

As the flame retardant, a phosphorus-containing flame retardant,nitrogen-containing flame retardant, halogen-containing flame retardant,metal hydroxide flame retardant such as an aluminum hydroxide, and thelike can be given. These flame retardants can be used eitherindividually or in combination of two or more.

As examples of the filler, inorganic fillers such as glass powder,carbon black, silica, talc, calcium carbonate, mica, alumina, titania,zirconia, mullite, cordierite, magnesia, clay, and barium sulfate andorganic fillers such as wood powder and polyethylene powder can begiven. If graphite powder, wood or bamboo charcoal powder, metal powder,and the like are used, conductivity and electromagnetic wave shieldingproperties can be increased. If powder of barium titanate, strontiumtitanate, lead titanate, magnesium titanate, bismuth titanate, leadzirconate, or the like is used, the relative dielectric constant can beincreased. If a ferromagnetic metal powder, for example, ferrite such asMn—Mg—Zn ferrite, Ni—Zn ferrite, or Mn—Zn ferrite; carbonyl iron,iron-silicon alloy, iron-aluminum-silicon alloy, iron-nickel alloy, orthe like is used, the resulting product is provided with ferromagneticproperties. Fillers with the surface treated with a silane couplingagent or the like may be used.

As the coloring agent, dyes, pigments, and the like can be used. Thereare a great number of types of dyes. Any dye appropriately selected fromamong various types of known dyes can be used in the present invention.As examples of the pigment, carbon black, graphite, chrome yellow, ironoxide yellow, titania, zinc oxide, trilead tetraoxide, minium, chromiumoxide, iron blue, and titanium black can be given. As examples of thelight stabilizer, benzotriazole UV absorbers, benzophenone UV absorbers,salicylate UV absorbers, cyano acrylate UV absorbers, oxalinide UVabsorbers, hindered amine UV absorbers, and benzoate UV absorbers can begiven.

Although not specifically limited, the amount of these additives to beadded is usually in the range of 0.001-500 parts by weight for 100 partsby weight of the thermoplastic resin.

As the method for producing the polymerizable composition (A) by bulkpolymerization, (a) a method of pouring or applying the polymerizablecomposition (A) onto a supporting body and polymerizing the compositionby bulk polymerization, (b) a method of polymerizing the polymerizablecomposition (A) in a mold, (c) a method of impregnating a textilematerial with the polymerizable composition (A) and polymerizing thecomposition by bulk polymerization, and the like can be given.

A thermoplastic resin film can be obtained if the method (a) isfollowed. As the supporting body used in this method, resins such aspolyethylene terephthalate, polypropylene, polyethylene, polycarbonate,polyethylenenaphthalate, polyallylate, and nylon; metals such as iron,stainless steel, copper, aluminum, nickel, chromium, gold, and silver;and the like can be given. Although there are no specific limitations tothe shape of the supporting body, a metal foil or a resin film ispreferably used. The thickness of the metal foil or resin film isusually 1-150 μm, preferably 2-100 μm, and still more preferably 3-75 μmfrom the viewpoint of workability and the like.

There are no specific limitations to the method of applying thepolymerizable composition (A) to the surface of the supporting body. Aspray coating method, dip coating method, roll coating method, curtaincoating method, die coating method, slit coating method, and the likecan be given.

Although not specifically limited, as the method of heating thepolymerizable composition (A) to a prescribed temperature, a method ofheating the composition by placing the supporting body on a heatingplate, a method of heating while applying pressure using a press machine(heat-press), a method of pressing using a heated roller, a method ofusing a furnace, and the like can be given.

The thickness of the thermoplastic resin film obtained in this manner isusually 15 mm or less, preferably 10 mm or less, and more preferably 5mm or less.

A thermoplastic resin molded product can be obtained if the method (b)is followed. The shape of the molded product includes a sheet, film,column, cylinder, and multiangular prism, for example.

A commonly known mold, for example, a split mold having a core andcavity can be used by injecting the reaction fluid to the cavity andeffecting the bulk polymerization therein. The core and cavity arefabricated so that a vacant space may be provided conforming to theshape of a desired molded product. There are no specific limitations tothe shape, material, and size of the mold. A molded product of thethermoplastic resin in the form of a sheet or film can also be obtainedby providing plate molds (e.g. glass boards or metal plates) and aspacer with a prescribed thickness, interposed between two sheets ofplate molds, injecting the reaction fluid to the space formed by the twosheets of plate molds and the spacer, and effecting the bulkpolymerization therein

The filling pressure (injection pressure) for filling the reaction fluidin the cavity of the mold is usually 0.01-10 MPa, and preferably 0.02-5MPa. If the filling pressure is too low, there is a tendency for thetransfer surface formed in the inner surface of the cavity not to betransferred in a good order. Too high a filling pressure requires ahighly rigid mold and is, therefore, uneconomical. The mold clampingpressure is usually within the range of 0.01-10 MPa.

The method (c) can produce a prepreg impregnated with a thermoplasticresin. The textile material used here is organic and/or inorganic fiberand includes, for example, known fibers such as glass fiber, carbonfiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber,polyester fiber, amide fiber, metal fiber, and ceramic fiber. Thesefibers can be used either individually or in combination of two or more.As the form of the textile material, a mat cloth, nonwoven fabric, andthe like can be given.

A textile material is impregnated with the polymerizable composition(A), for example, by a method comprising applying a prescribed amount ofthe polymerizable composition (A) to the textile material by a knownmethod such as spray coating, dip coating, roll coating, curtaincoating, die coating, or slit coating, layering a protective film overthe coated polymerizable composition (A), as required, and pressing theresulting material using a roller or the like. After the textilematerial has been impregnated with the polymerizable composition (A),the resulting product (impregnated material) is heated to a prescribedtemperature to polymerize the composition (A) by bulk polymerization,whereby a thermoplastic resin-impregnated prepreg can be obtained.

There are no specific limitations to the method of heating theimpregnated material. For example, the above-mentioned method (a) can beapplied, in which case the impregnated material placed on a supportingbody may be heated. Alternatively, it is possible to impregnate thetextile material which is placed in the mold in advance with thepolymerizable composition (A), then follow the method (b) for bulkpolymerization of the composition.

Since the polymerizable composition (A) has a low viscosity as comparedwith a conventional resin varnish, the composition can cause the textilematerial to be excellently impregnated therewith. The resulting prepregthus contains the textile material homogeneously impregnated with thethermoplastic resin. Because the prepreg can be obtained by impregnatingthe textile material with the polymerizable composition (A), followed byheating for bulk polymerization, the manufacturing process does notrequire a step of removing a solvent from the impregnated resin varnishthat was indispensable in the conventional process. The processtherefore exhibits good productivity and is free from problems such asodor, blister, and the like due to a residual solvent. Furthermore,since the thermoplastic resin of the present invention is excellent instorage stability, the resulting prepreg is also excellent in storagestability.

In any of the above methods (a), (b), and (c), the heating temperaturefor polymerizing the polymerizable composition (A) is usually 50-200°C., and preferably 100-200° C. The polymerization time is usually 10seconds to 20 minutes, and preferably within 5 minutes.

The polymerization reaction begins when the polymerizable composition(A) is heated to a predetermined temperature. This polymerizationreaction is an exothermic reaction. Thus, once the bulk polymerizationbegins, the temperature of the reaction solution will rapidly increaseand reach a peak temperature in a short time (for example, about 1second to 5 minutes). If the temperature during the polymerizationreaction is too high, the crosslinking reaction proceeds in addition tothe polymerization reaction, thereby making it difficult to obtain thepost-crosslinkable thermoplastic resin. Therefore, it is necessary toensure that only the polymerization reaction proceeds and to inhibit thecrosslinking reaction. Specifically, the peak temperature of bulkpolymerization should be controlled usually to less than 230° C., andpreferably less than 200° C.

When a radical generating agent is used as the crosslinking agent, it ispreferable to control the peak temperature of the bulk polymerization tothe one minute half-life temperature of the radical generating agent.The one minute half-life temperature here refers to the temperature atwhich one half of the radical generating agent decomposes in one minute.For example, the one minute half-life temperature of di-t-butylperoxideis 186° C. and that of 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexine is194° C.

To prevent overheating due to the heat of the polymerization reaction,it is possible to retard the reaction by adding a reaction retarder tothe polymerizable composition (A).

As examples of the reaction retarder that can be used, chain 1,5-dienecompounds such as 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis,cis)-2 6-octadiene, (cis, trans)-2,6-octadiene, (trans,trans)-2,6-octadiene; chain 1,3,5-triene compounds such as(trans)-1,3,5-hexatriene, (cis)-1,3,5-hexatriene,(trans)-2,5-dimethyl-1,3,5-hexatriene,(cis)-2,5-dimethyl-1,3,5-hexatriene; phosphines such as triphenylphosphine, tri-n-butyl phosphine, and methyl diphenylphosphine; andLewis bases such as aniline can be given.

Among the above-mentioned cycloolefin monomers, those having a 1,5-dienestructure or 1,3,5-triene structure in the molecule functions as areaction retarder, Examples of such cycloolefin monomers includemonocyclic compounds such as 1,5-cyclooctadiene,1,5-dimethyl-1,5-cyclooctadiene, 1,3,5-cycloheptatriene, (cis, trans,trans)-1,5,9-cyclododecatriene, 4-vinylcyclohexene, and dipentene;polycyclic compounds such as 5-vinyl-2-norbornene,5-isopropenyl-2-norbornene, and 5-(1-propenyl)-2-norbornene; and thelike.

When the reaction retarder is added, the amount is usually in the rangeof 0.001-5 wt %, and preferably 0.002-2 wt % of the monomer solutions.If the amount of the reaction retarder is less than 0.001 wt %, thereaction retarding effect is not exhibited. If the amount is more than 5wt %, on the other hand, the product properties may be impaired due tothe reaction retarder which remains in the polymer. There is also apossibility that the polymerization reaction may not sufficientlyproceed.

The thermoplastic resin of the present invention is obtained by themanufacturing method of the present invention and is post-crosslinkable.The term “post-crosslinkable” herein refers to properties of athermoplastic resin of being crosslinked when heated, melted, andcontinuously heated to produce a crosslinked resin.

Since the bulk polymerization has almost completely proceeded, thethermoplastic resin of the present invention contains only a smallamount of unreacted monomers. In other words, since the polymerizationreaction rate is high, the resin does not worsen the work environmentdue to an odor originating from monomers. The polymerization reactionrate of the thermoplastic resin of the present invention is usually 80%or more, more preferably 90% or more, and still more preferably 95% ormore. The polymerization reaction rate of the thermoplastic resin can bedetermined by dissolving the thermoplastic resin in a solvent andanalyzing the resulting solution using gas chromatography, for example.

Dissolution of the resin produced by bulk polymerization in a solventcan confirm that the resin is a thermoplastic resin. Specifically, aresin is a thermoplastic resin if dissolved in a solvent and acrosslinked resin if not dissolved in a solvent. As examples of thesolvent, aromatic hydrocarbons such as benzene and toluene; ethers suchas diethyl ether and tetrahydrofuran; and halogenated hydrocarbons suchas dichloromethane and chloroform can be given.

The thermoplastic resin of the present invention is not necessarily apost-crosslinkable thermoplastic resin in its entirety, but a partiallycrosslinked resin is acceptable. When a molded resin product with acertain thickness is produced from the thermoplastic resin by bulkpolymerization, the polymerization reaction temperature is partiallyincreased in the center of the molded product due to difficulty inreleasing the heat of polymerization reaction from the center section.In such a case, the problem can be obviated if the thermoplastic resinis post-crosslinkable at least on the surface of the molded product.

Since the bulk polymerization has almost completely proceeded in thethermoplastic resin of the present invention, the bulk polymerization(metathesis ring-opening polymerization) does not proceed during storingof the thermoplastic resin. Even if the polymerizable composition (A)contains a crosslinking agent, the crosslinking reaction does notproceed unless the resin is heated. Since the surface hardness changesonly with difficulty during preservation, such a thermoplastic resinpossesses excellent storage stability. Particularly, when thepolymerizable composition (A) contains a radical generating agent and aradical crosslinking retarder as the crosslinking agent, thethermoplastic resin obtained by bulk polymerization is excellent instorage stability.

-   2) Method for Manufacturing Crosslinked Resin

The method for manufacturing the crosslinked resin of the presentinvention is characterized by comprising a step of crosslinking thethermoplastic resin of the present invention. Specifically, thecrosslinked resin can be obtained by melting and heating thethermoplastic resin of the present invention and continuing heating toeffect the crosslinking reaction. The temperature for crosslinking thethermoplastic resin of the present is higher than the peak temperatureof bulk polymerization preferably at least 20° C., usually 170-250° C.,and more preferably 180-220° C. Although there are no specificlimitations, the crosslinking time is usually from several minutes toseveral hours.

There are also no specific limitations to the method for crosslinkingthe thermoplastic resin insofar as the crosslinking operation comprisesmelting the thermoplastic resin. When the thermoplastic resin is moldedin the form of a sheet or film, the sheets or films are preferablylaminated and heat-pressed, if necessary. The pressure applied forpress-heating is usually 0.5-20 MPa, and preferably 3-10 MPa. Excellentproductivity of heat-press is attained by using a known pressing machinehaving a press frame mold for forming plates, a press-forming machinesuch as an SMC (sheet mold compound) or a BMC (bulk mold compound), andthe like.

-   3) Method for Manufacturing Crosslinked Resin Composite Material

The method for manufacturing a crosslinked resin composite material ofthe present invention comprises a step of laminating the thermoplasticresin of the present invention on the substrate and crosslinking thethermoplastic resin portion.

As the substrate, metal foils such as a copper foil, aluminium foil,nickel foil, chromium foil, gold foil, and silver foil; a printedcircuit board; films such as a conductive polymer film and other resinfilms; and the like can be given. When the thermoplastic resin wasmanufactured by the above method (a), the supporting body may be used asis as the substrate.

Although there are no specific limitations to the method of crosslinkingthe thermoplastic resin portion, a method of heat-pressing thethermoplastic resin laminated on the substrate is preferable formanufacturing the crosslinked resin composite material with sufficientproductivity. The same heat-press conditions as mentioned for themanufacturing method of the crosslinked resin are applicable.

Because the thermoplastic resin of the present invention to be used isexcellent in flowability and adhesion, a crosslinked resin compositematerial excelling in flatness, consisting of firmly adhered substrateand crosslinked resin, and exhibiting superior adhesiveness can beobtained by laminating the thermoplastic resin on the substrate andcrosslinking the thermoplastic resin.

The method of manufacturing the crosslinked resin composite material ofthe present invention is suitable for producing a metal clad laminateusing a metal foil, preferably a copper foil as the substrate. Thethickness and surface roughness of the metal foil can be appropriatelydetermined according to the purpose of application without any specificlimitations. The surface of the metal foil may be treated with a silanecoupling agent, a thiol coupling agent, a titanate coupling agent, orvarious types of adhesive, preferably with a silane coupling agent ofthe following formula (1) or a thiol coupling agent of the followingformula (2).RSiXYZ  (1)T(SH)_(n)  (2)

In the formula (1) for a silane coupling agent, R is a group having adouble bond, a mercapto group, or an amino group at the terminal, X andY individually represent a hydrolyzable group, a hydroxyl group, or analkyl group, Z represents a hydrolyzable group or a hydroxyl group.

As specific examples of the silane coupling agent of the formula (1),allyltrimethoxysilane, 3-butenyltrimethoxysilane,styryltrimethoxysilane,N-β-(N-(vinylbenzyl)aminoethyl)-γ-aminopropyltrimethoxysilane and itssalt, allyltrichlorosilane, allylmethyldichlorosilane,styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane,vinyltrichlorosilane, β-methacryloxyethyltrimethoxysilane,β-methacryloxyethyltriethoxysilane,γ-methacryloxypropyltrimethoxysilane,β-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and the like can begiven.

In the formula (2) for a thiol coupling agent, T represents an aromaticring, an aliphatic ring, a heterocyclic, or an aliphatic chain, and n isan integer of 2 or more.

As examples of the thiol coupling agent,2,4,6-trimercapto-1,3,5-triazole,2,4-dimercapto-6-dibutylamino-1,3,5-triazine,2,4-dimercapto-6-anilino-1,3,5-triazine, and the like can be given.

If the thermoplastic resin of the present invention is laminated with ametallic foil and heat-pressed, a thermoplastic resin portion is meltedand is caused to adhere with a metallic foil, then the crosslinkingreaction proceeds to obtain a crosslinked resin. A crosslinkedresin-metal clad laminate in which the crosslinked resin and metal foilis firmly bonded can be obtained using the manufacturing method of thepresent invention. The peel-off strength of the metal foil from theresulting crosslinked resin-metal clad laminate measured according toJIS C6481 is preferably 0.8 kN/m or more, and more preferably 1.2 kN/mor more.

The method for manufacturing the crosslinked resin composite material ofthe present invention is also suitable for producing a multilayerprinted circuit board using a printed circuit board as the substrate.Any known printed wiring boards commonly used for a circuit can be usedwithout specific limitations as the printed circuit board. A multilayerprinted circuit board can be manufactured by layering an outer layermaterial (e.g. one side copper clad laminate) and an inner layermaterial (e.g. both-side printed circuit board) via a prepreg andpress-heating of the layered materials.

Since the crosslinked resin composite material obtained by the presentinvention consists of a crosslinked resin with excellent electricinsulation property, mechanical strength, heat resistance, dielectricproperty, and the like, firmly adhered with a substrate with excellentadhesion, the material is suitable as an electric material.

A printed circuit board in which the crosslinked resin with excellentelectric insulation property, mechanical strength, and adhesion, firmlyadhered with a printed circuit board, can be efficiently manufactured bythe present invention.

EXAMPLES

The present invention will now be described in detail by way of examplesand comparative examples, which should not be construed as limiting thepresent invention. In the examples and comparative examples below“parts” and “%” are indicated on the weight basis, unless otherwisespecified.

The strength for peeling a copper foil from a copper clad laminate, theflexural strength after peeling the copper foil, and the modulus ofbending elasticity were measured according to JIS C6481.

Reference Example 1 Preparation of Catalyst Solution

A catalyst solution was prepared by dissolving 51 parts ofbenzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine) ruthenium dichloride, and 79 parts oftriphenylphosphine in 952 parts of toluene in a glass flask.

Example 1

A glass flask was charged with a monomer solution of 2,800 parts oftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, 1,200 parts of5-ethylidene-2-norbornene, and 6,000 parts of dicyclopentadiene, and 909parts of styrene as a chain transfer agent. Then, 39 parts of the abovecatalyst solution was added with stirring to obtain a polymerizablecomposition a.

This composition a was instantaneously cured when injected onto an ironplate heated at 150° C. The cured product was immediately removed fromthe iron plate to obtain a polymer in the form of an odorless film. Thefilm had a thickness of 0.1 mm and was soluble in toluene, indicatingthat the polymer was not crosslinked. The amount of residual monomers ina toluene solution of the film was measured using gas chromatography toconfirm that the polymerization reaction rate was 98.9%.

After preserving the film for one week at room temperature in the air,the polymerization reaction rate was determined using the same method asabove. The polymerization reaction rate was 98.9%, indicating that thereaction did not proceed after preparation of the film.

Example 2

The film obtained in Example 1 was placed on a plate heated at 200° C.Once melted on the plate, the film became non-flowable due tocrosslinking. The resulting polymer was not dissolved in toluene,confirming that the polymer was crosslinked.

Comparative Example 1

A film was prepared in the same manner as in Example 1, except thatstyrene was not added. The resulting film was not dissolved in toluene.

It was confirmed from the results of Example 1 and Comparative Example 1that a chain transfer agent such as styrene is required to obtain apost-crosslinkable thermoplastic resin.

Comparative Example 2

The experiment was carried out in the same manner as in comparativeExample 1, except that the iron plated was heated to 60° C. and thepolymer was cured for 20 minutes on the iron plate. The resulting filmhad an odor of monomers. In the same manner as in Example 1, thepolymerization reaction rate was determined immediately afterpreparation of the film and after storing the film for one week toconfirm that the polymerization reaction rate was 76% and 85%,respectively. It was thus found that the reaction proceeded duringstoring.

Comparative Example 3

The polymerizable composition a prepared in the same manner as inExample 1 was put into a glass flask. The glass flask was placed in awater bath at 50° C. to cure the composition. The internal temperatureof the flask increased to 235° C. due to the heat of polymerization, Theresulting polymer was not dissolved in toluene. The polymer was placedon a heated plate at 200° C. to confirm that the polymer did not melt.

The result indicated that if the polymer is overheated during thepolymerization, a crosslinking reaction occurs and a thermoplastic resincannot be obtained.

Example 3

A bottle made of polyethylene was charged with 45 parts ofdicyclopentadiene, 5 parts of norbornene, 0.45 part of styrene, and0.197 part of the catalyst solution obtained in Reference Example 1, inthat order, while stirring to obtain a polymerizable composition b.

The composition b was sent to a metal mold under pressure. The metalmold is for fabrication of a flat board with a size of 2.2 mm×120 mm×120mm, consisting of two sheets of chromium-plated iron boards equippedwith a heater and a spacer with a shape of a Japanese character ko (

) interposed between the boards. One side of the metal mold is heated to68° C. and the other side to 50° C.

Two minutes after pressure filling the polymerizable composition b inthe mold, the molded product was opened to remove the molded flat board.The flat board was cut into a disk with a diameter of 10 mm and the diskwas dipped in toluene for one day to confirm that the surface wasdissolved but the center portion along the thickness remainedundissolved. The result indicates that crosslinking proceeded in thecenter of the flat board, while the surface remained without beingcrosslinked.

The flat board obtained was cut into an 87 mm×87 mm square. Anelectrolysis copper foil (Type GTS, thickness 0.018 mm, manufactured byFurukawa Circuit Foil Co., Ltd.) was layered on one side (the side onwhich the mold was heated to 68° C. during polymerization) of the squareflat board using a rectangular mold for forming a flat board (size: 2mm×90 mm×90 mm) and heat-pressed to obtain a one side copper cladlaminate with a board thickness of 2 mm. The heat-press was carried outat a press temperature of 200° C. for 15 minutes under a pressure of 5MPa.

The peel-off strength of the copper foil from the resulting copper cladlaminate was 1.6 kN/m.

After measuring the copper foil peel-off strength, the resin portionafter removing the copper foil was cut into a disk with a diameter of 10mm. The disk was dipped in toluene for one day to confirm that nodissolution of the surface occurred, but the disk only swelled in itsentirety.

The results indicate that the heat-press operation melted the resinsurface, caused the resin to adhere to the copper foil, and the resincrosslinked thereafter.

Comparative Example 4

A flat board was prepared in the same manner as in Example 3, exceptthat styrene was not added. The flat board obtained was cut into a diskwith a diameter of 10 mm and the disk was dipped in toluene for one day.It was confirmed that no surface dissolution as that observed in Example3 occurred, but the disk swelled in its entirety.

A one-side copper clad laminate with a board thickness of 2 mm wasprepared in the same manner as in Example 3 using the above flat board.The copper foil peel-off strength of the copper foil from the resultingcopper clad laminate was measured and found that the peel-off strengthwas 0.2 kN/m.

A crosslinked resin-copper clad laminate in which a copper foil and thecrosslinked resin firmly bonded was obtained in Example 3. However, inComparative Example 4 in which no chain transfer agent was added,thermoplasticity was not exhibited even on the surface. The crosslinkedresin-copper clad laminate obtained by layering a copper foil and theresulting resin, followed by heat-press was found to exhibit only weakadhesion of the copper foil to the crosslinked resin.

Example 4

A polyethylene bottle was charged with a monomer solution of 38.5 partsof tetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene and 18.5 parts of5-ethylidene-2-norbornene, 0.39 part of styrene as a chain transferagent, 0.51 part of di-t-butylperoxide (one minute half-lifetemperature: 186° C.) as a crosslinking agent, and 0.197 part of theabove catalyst solution with stirring to obtain a polymerizablecomposition c.

A flat board was prepared from the composition c in the same manner asin Example 3. The flat board obtained was cut into a disk with adiameter of 1 mm and the disk was dipped in toluene for one day toconfirm that the surface was dissolved but the center portion along thethickness remained without being dissolved. The result indicates thatcrosslinking proceeded in the center of the flat board, while thesurface remained without being crosslinked.

The disc was chipped for a depth of 0.2 mm from the surface on bothsides and the chipped material was dissolved in toluene. The amount ofremaining unreacted monomers was measured by gas chromatography analysisto determined the rate of polymerization reaction, which was found to be95%.

A one-side copper clad laminate with a board thickness of 2 mm wasprepared in the same manner as in Example 3 using the flat boardobtained. The peel-off strength of the copper foil from the resultingcopper clad laminate was 1.2 kN/m.

After measuring the copper foil peel-off strength, the resin portionafter removing the copper foil was cut into a disk with a diameter of 10mm. The disk was dipped in toluene for one day to confirm that nodissolution of the surface occurred, while the disk only swelled in itsentirety. The resin portion without the copper foil after measuring thecopper foil peel-off strength was allowed to float in a solder bath at260° C. for 20 seconds to confirm that neither gas generation nordeformation was seen.

The results indicate that the heat-press operation melted the resinsurface, caused the resin to adhere to the copper foil, and the resincrosslinked thereafter to produce a crosslinked resin with high heatresistance.

Comparative Example 5

A flat board with a thickness of 2.2 mm was prepared in the same manneras in Example 4, except that di-t-butyl peroxide was not added. Aone-side copper clad laminate with a board thickness of 2 mm wasprepared in the same manner as in Example 4 using the flat boardobtained. The peel-off strength of the copper foil from the one-sidecopper clad laminate was 1.1 kN/m.

After measuring the copper foil peel-off strength, the resin portionafter removing the copper foil was cut into a disk with a diameter of 10mm. The disk was dipped in toluene for one day to confirm that the diskwas completely dissolved. The resin portion without the copper foilafter measuring the copper foil peel-off strength was allowed to floatin a plating bath at 260° C. for 20 seconds to confirm that the materialmelted and deformed, and that gas was generating from the surface. Theabove experiments confirmed that when a cycloolefin having two or moremetathesis ring-opening reaction sites was not used and a crosslinkingagent such as di-t-butyl peroxide was not added, a cross-linkingreaction did not proceed even if the thermoplastic resin was heated andmelted, thereby not obtaining a crosslinked resin. The copper cladlaminate board obtained exhibited only poor heat resistance.

Comparative Example 6

A flat board with a thickness of 2.2 mm was prepared in the same manneras in Example 4, except that styrene was not added. The flat boardobtained was cut into a disk with a diameter of 10 mm and the disk wasdipped in toluene for one day. It was confirmed that surface dissolutionas that observed in Example 4 did not occur, but the disk swelled in itsentirety.

A one-side copper clad laminate with a board thickness of 2 mm wasprepared in the same manner as in Example 4 using the above flat board.The peel-off strength of the copper foil from the one-side copper cladlaminate board was 0.2 kN/m.

The results indicate that when no chain transfer agent such as styreneis added, a thermoplastic resin cannot be obtained and the resultingresin cannot allow a copper foil to melt and adhere thereto.

Example 5

A glass bottle was charged with 25 parts oftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, 8 partsoftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-9-ene-4-carboxylic acid, 8.2parts of brominated bisphenol A epoxy resin (epoxy equivalent: 420-480g/eq, “AER8049” manufactured by Ciba Specialty Chemicals Co.), 4.9 partsof hydrogenated bisphenol A epoxy resin (epoxy equivalent: 210 g/eq,“EXA-7015” manufactured by Dainippon Ink and Chemicals, Inc.), and 0.2part of styrene as a chain transfer agent. The mixture was heated andstirred in an oil bath at 80° C. to obtain a monomer mixture 1.

A stirrer was put into the glass bottle and 0.013 part of benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)rutheniumdichloride and 0.00062 part of triphenylphosphine were added. After theaddition of 0.013 part of toluene to dissolve the mixture, 3 parts ofthe monomer mixture 1 obtained above was added with vigorous stirring toobtain a polymerizable composition d, which was heated in a water bathat 60° C. After 47 seconds, mist generation due to polymerization heatwas observed and the polymerization reaction was completed.

The resulting polymer did not dissolve in tetrahydrofuran indicatingthat the polymer was not crosslinked. A part of the polymer wasdissolved in tetrahydrofuran to measure the amount of residual monomersusing gas chromatography to confirm that the polymerization reactionrate was 91%. The polymer was gradually heated on a heater plate. It wasconfirmed that the polymer became fluid at 210° C., but when thetemperature was increased, lost fluidity and became rubbery at 250° C.

Example 6

An eggplant flask was charged with 26 parts of1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene, 4.2 parts of5-norbornene-2,3-dicarboxylic acid anhydride, 5.2 parts of brominatedbisphenol A epoxy resin (AERS049), 3.1 parts of hydrogenated bisphenol Aepoxy resin (EXA-7015), and 0.18 part of styrene as a chain transferagent. The mixture was heated and stirred in an oil bath at 80° C. toobtain a monomer mixture 2.

A stirrer was put into the glass bottle and 0.024 part of benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)rutheniumdichloride and 0.0037 part of triphenylphosphine were added. After theaddition of 0.013 part of toluene to obtain a homogeneous solution, 3parts of the monomer mixture 2 obtained above was added with vigorousstirring to obtain a polymerizable composition e, which was heated in awater bath at 70° C. After 47 seconds, mist generation due topolymerization heat was observed and the polymerization reaction wascompleted.

The resulting polymer was dissolved in chloroform indicating that thepolymer was thermoplastic (not crosslinked). The amount of residualmonomers in the polymer solution was measured by gas chromatography toconfirm that the reaction rate of norbornene monomers(1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene and5-norbornene-2,3-dicarboxylic acid anhydride) was 98%. The polymer wasgradually heated on a heater plate. It was confirmed that the polymerbecame fluid at 170° C., but when the temperature was increased, lostfluidity and became rubbery at 230° C.

Example 7

A polyethylene bottle was charged with 0.2089 part of3,5-di-t-butylhydroxyanisol, 22.5 parts oftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, 7.5 parts of2-norbornene, 0.69 part of allyl methacrylate, 0.443 part ofdi-t-butylperoxide (one minute half-life temperature: 186° C.), and 0.1part of the catalyst solution prepared in Reference Example 1 withstirring to obtain a polymerizable composition f.

Three sheets of glass cloth (each sheet cut into a size of 200 mm×200mm, thickness: 0.092 mm, Product #2116/350/AS891AW, manufactured byAsahi-Schwebel Co., Ltd.) were placed on a glass fiber-reinforcedpolytetrafluoroethylene resin (PTFE resin) film (300 mm×300 mm×0.08 mm,Product #5310, manufactured by Saint-Gobain K. K.). About half an amountof the polymerizable composition f was poured onto the glass cloth,which was then covered with another glass fiber-reinforced PTFE resinfilm, followed by pressing with a roller to cause the glass cloth sheetsto be impregnated with the composition.

Each side of the glass fiber-reinforced PTFE resin film was attached toan aluminum plate heated at 145° C. for one minute to polymerize thepolymerizable composition f. Thereafter, the glass fiber-reinforced PTFEresin films were removed from both sides to obtain a prepreg.

A part of the prepreg was put into a platinum crucible and the resinportion was burnt in an electric furnace. The glass content determinedfrom the glass weight of the unburnt portion was 58%. Apart of theprepreg was dipped into toluene to dissolve the resin portion. Theamount of residual monomers in the solution was determined by gaschromatography. Based on the resulting amount of residual monomers andthe glass content, the polymerization reaction rate was calculated to be97%.

0.05 part of acetic acid was added to 60 parts of distilled water. Afterthe addition of 0.18 part of vinyl tris(2-methoxyethoxy)silane (“A-172”manufactured by Nippon Unicar Co., Ltd.), the mixture was stirred for 10minutes to hydrolyze and dissolve the vinyl tris(2-methoxyethoxy)silane,thereby obtaining a silane coupling agent solution. Using absorbentcotton impregnated with the silane coupling agent solution, the silanecoupling agent solution was applied to a rough surface of anelectrolysis copper foil (GTS-treated rough surface, thickness: 0.018mm, manufactured by Furukawa Circuit Foil Co., Ltd.) and dried for onehour at 130° C. under nitrogen atmosphere.

Three sheets of prepreg (each cut into a size of 87 mm×87 mm) wereinserted in a square frame (inner size: 90 mm×90 mm, thickness: 1 mm). Acopper foil (cut into a size of 115 mm×115 mm) treated with the silanecoupling agent was attached to the top and bottom of the rough surfacesof the prepreg sheet, followed by heat-pressing for 15 minutes at 4.1MPa and 200° C. After cooling to 100° C. or less while applying thepressure, the sample was removed to obtain a both-side copper cladlaminate.

The peel-off strength of the copper foil from the resulting both-sidecopper clad laminate was measured and found that the peel-off strengthwas 1.6 kN/m. The solder heat resistance test was carried out in asolder bath at 260° C. for 20 seconds to confirm that no swelling wasobserved.

After removing the copper foil, the bending test of the fiber-reinforcedresin portion (thickness: 1.5 mm) was carried out to find that thebending modulus of elasticity was 12 GPa and the bending strength was385 MPa. The dielectric constant and dielectric loss tangent weremeasured using an impedance analyzer (“E4991” manufactured by AgilentTechnologies) to find that dielectric constant and dielectric losstangent were respectively 3.5 and 0.0013 at 100 MHz and 3.5 and 0.0022at 13.1 GHz.

Example 8

A polyethylene bottle was charged with 0.6 part of fumed silica(“AEROSIL 200” manufactured by AEROSIL Japan Inc.), 22.5 parts oftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, 7.5 parts of2-norbornene, 1.0 part of styryl methacrylate, 0.36 part of2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexine (one minute half-lifetemperature: 194° C.), and 0.11 part of the catalyst solution preparedin Reference Example 1 with stirring to obtain a polymerizablecomposition g.

0.05 part of acetic acid was added to 60 parts of distilled water. Afterthe addition of 0.18 part of styryl trimethoxysilane (“KEM-1403”manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture was stirredfor one hour to hydrolyze and dissolve the styryl trimethoxysilane,thereby obtaining a silane coupling agent solution. Using absorbentcotton impregnated with the silane coupling agent solution, the silanecoupling agent solution was applied to a rough surface of anelectrolysis copper foil (the same copper foil as used in Example 7) anddried for one hour at 130° C. under nitrogen atmosphere.

The polymerizable composition g was applied to the rough surface of theabove electrolysis copper foil (cut into 220 mm×220 mm) using a coatingroller. The coated surface was covered with a glass-fiber reinforcedPTFE resin film (the same film as used in Example 7). The copper foilside was attached for one minute to an aluminum plate heated to 145° C.to polymerize the composition. Thereafter, the glass fiber-reinforcedPTFE resin film was removed to obtain a resin-attached copper foil.

A part of the resin-attached copper foil was dipped into toluene todissolve the resin portion. The amount of residual monomers in thesolution was determined by gas chromatography. Based on the resultingamount of residual monomers and the weight of the remaining copper foil,the polymerization reaction rate was calculated to be 97%.

The resin-attached copper foil was attached to both sides of a glassepoxy both-side copper clad laminate (thickness: 1 mm, size 80 mm×80 mm)microetched using a surface roughener CZ-8100 (LEC Co., Ltd.), with theresin being on the inner side, and the resulting material washeat-pressed at 5.2 MPa and 200° C. for 15 minutes. After cooling to100° C. or less while applying the pressure, the sample was removed toobtain a multilayer copper clad laminate.

The peel-off strength of the bottom side copper foil from the resultingmultilayer copper clad laminate was measured and found that the peel-offstrength was 1.6 kN/m. The surface resin after removing the copper foilwas subjected to the peel-off adhesion test according JIS K5400 todetermine adhesion between the resin surface and the inner side copperfoil. As a result, there was no peel-off.

Copper was removed from a both-side copper clad laminate prepared in thesame manner as in Example 7 by etching using an aqueous solution ofammonium persulfate (thickness: 1.4 mm, size 80 mm×80 mm) and the aboveresin-attached copper foil was attached to both sides of the copper-freelaminate board, with the resin being on the inner side, and theresulting material was heat-pressed at 5.2 MPa and 200° C. for 15minutes. After cooling to 100° C. or less while applying pressure, thesample was removed to obtain a both side copper clad laminate.

The peel-off strength of the top side copper foil from the resultingboth-side copper clad laminate was measured and found that the peel-offstrength was 1.6 kN/m. The surface resin after removing the copper foilwas subjected to the peel-off adhesion test according JIS K5400 todetermine adhesion between the resin surface and the inner side copperfoil. As a result, there was no peel-off.

Example 9

A polyethylene bottle was charged with 0.6 part of fumed silica(“AEROSIL 200”), 12 parts oftetracyclo[6.2.1.1^(3,6)0.0^(2,7)]dodec-4-ene, 5.4 parts of2-norbornene, 12 parts of dicyclopentadiene, 0.36 part of styrene, and0.34 part of di-t-butylperoxide. 0.11 part of the catalyst solutionprepared in Reference Example 1 was added with stirring to obtain apolymerizable composition h.

The polymerizable composition h was applied to the upper surface of aglass-fiber reinforced PTFE resin film (the same film as used in Example7) using a coating roller. The coated surface was covered with anotherglass-fiber reinforced PTFE resin film. The copper foil side wasattached for one minute to an aluminum plate heated to 145° C. topolymerize the composition. Thereafter, the glass fiber-reinforced PTFEresin film was removed to obtain a resin film.

A part of the film was dipped into toluene to dissolve the resinportion. The amount of residual monomers in the solution was determinedby gas chromatography. Based on the resulting amount of residualmonomers, the polymerization reaction rate was calculated to be 98%.

A both-side copper clad laminate with a crosslinked resin adheringthereto was prepared in the same manner as in Example 8, except forusing the resin film obtained above. The peel-off adhesion testaccording JIS K5400 was carried out on the surface of the resin layer.As a result, there was no peel-off.

Examples 10-15

Experiments were carried out in the same manner as in Example 7 usingthe silane coupling agents shown in Table 1. The results of the peel-offstrength of the copper foil from the resulting both-side copper cladlaminate are shown in Table 1. In Examples 12 and 15, the silanecoupling agent solutions prepared without using acetic acid were used.

Example 16

The same experiment as in Example 7 was carried out, except for using a0.3% tetrahydrofuran solution of 2,4,6-trimercapto-1,3,5-triazineinstead of the silane coupling agent solution. The results of thepeel-off strength of the copper foil from the resulting both-side copperclad laminate are shown in Table 1.

Copper foil peel-off strength Example Coupling agent (kN/m) 7vinyltris(2-methoxyethoxy)silane 1.5 10 Allyltrimethoxysilane 1.6 11styryl trimethoxysilane 1.5 12 N-β-(N-(vinylbenzyl)aminoethyl)-γ- 1.5aminopropyltrimethoxysilane hydrochloride 13δ-methacryloxybutyltrimethoxysilane 1.5 14γ-mercaptopropyltrimethoxysilane 0.9 15N-β-(aminoethyl)-γ-aminopropyltrimethoxy- 0.6 silane 162,4,6-trimercapto-1,3,5-triazine 1.3

Examples 17-19

Experiments for 17 to 19 were carried out in the same manner as inExample 11, except for using styryl methacrylate (Example 17), 1-octene(Examples 18), or styrene (Examples 19) instead of allyl methacrylate asa chain transfer agent. The copper foil peel-off strength wasrespectively 1.5 kN/m, 1.1 kN/m, and 1.1 kN/m.

The results indicate that the use of a chain transfer agent having amethacryloyl group increases the adhesion force of the copper foil withthe resin.

INDUSTRIAL APPLICABILITY

According to the present invention, a thermoplastic resin free from anodor of remaining monomers and excelling in storage stability can beobtained efficiently by a simple method of polymerizing a polymerizablecomposition (A) comprising (I) a cycloolefin (α) or a monomer solutioncontaining a norbornene monomer and a crosslinking agent, (II) ametathesis polymerization catalyst, and a chain transfer agent (III) bybulk polymerization. Since the methods of manufacturing the crosslinkedresin and the crosslinked resin composite material of the presentinvention are simple and can continuously manufacture the products, themethods are industrially advantageous. The crosslinked resin obtained bythe present invention is excellent in electric insulation property,mechanical strength, heat resistance, dielectric property, and the like.According to the present invention, a crosslinked resin compositematerial, wherein the composite material is obtained by laminating thethermoplastic resin of the present invention on a substrate andcrosslinking the thermoplastic resin, excels in adhesion between thecrosslinked resin and substrate, and is useful as an electrical materialand the like.

1. A method for manufacturing a post-crosslinkable thermoplastic resincomprising polymerizing a polymerizable composition (A) comprising anorbornene monomer, a metathesis polymerization catalyst, a chaintransfer agent, and an epoxy compound, wherein said polymerizablecomposition (A) is polymerized by bulk polymerization.
 2. The methodaccording to claim 1, wherein the maximum temperature during bulkpolymerization is less than 230° C.
 3. The method according to claim 1,wherein the polymerization conversion ratio is 80% or more.
 4. Themethod according to claim 1, wherein the chain transfer agent is acompound represented by the formula CH₂═CH-Q, wherein Q is a group whichhas at least one group selected from the group consisting of amethacryloyl group, acryloyl group, vinyl silyl group, epoxy group, andamino group.
 5. A post-crosslinkable thermoplastic resin produced by themethod according to claim
 1. 6. The thermoplastic resin according toclaim 5, wherein the thermoplastic resin is molded into a film bypolymerizing the polymerizable composition (A) on a supporting body bybulk polymerization.
 7. The thermoplastic resin according to claim 6,wherein the supporting body is a metal foil or a resin film.
 8. Thethermoplastic resin according to claim 5, wherein the thermoplasticresin is molded into a prescribed form by polymerizing the polymerizablecomposition (A) in a mold by bulk polymerization.
 9. The thermoplasticresin according to claim 5, obtained by impregnating a textile materialwith the polymerizable composition (A) and polymerizing thepolymerizable composition (A) by bulk polymerization.
 10. A method forproducing a crosslinked thermoplastic resin comprising crosslinking thethermoplastic resin according to any one of claims 5 to
 9. 11. A methodfor producing a crosslinked resin composite material comprising a stepof laminating the thermoplastic resin according to any one of claims 5to 9 on a substrate and crosslinking the thermoplastic resin portion.12. The method according to claim 11, wherein the substrate is a metalfoil.
 13. The method according to claim 12, wherein the metal foil ispreviously treated with a silane coupling agent of the following formula(1) or a thiol coupling agent of the following formula (2),RSiXYZ  (1)T(SH)_(n)  (2) wherein R is a group having a double bond, a mercaptogroup, or an amino group at the terminal end thereof, X and Yindividually represent a hydrolyzable group, a hydroxyl group, or analkyl group, Z represents a hydrolyzable group or a hydroxyl group, Trepresents an aromatic ring, an aliphatic ring, a heterocyclic, or analiphatic chain, and n is an integer of 2 or more.
 14. The methodaccording to claim 11, wherein the substrate is a printed circuit board.